CN117004073A - High-efficiency plastic photo-grafting treatment method and plastic metallization method - Google Patents
High-efficiency plastic photo-grafting treatment method and plastic metallization method Download PDFInfo
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- CN117004073A CN117004073A CN202311050278.5A CN202311050278A CN117004073A CN 117004073 A CN117004073 A CN 117004073A CN 202311050278 A CN202311050278 A CN 202311050278A CN 117004073 A CN117004073 A CN 117004073A
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- Prior art keywords
- grafting
- solution
- cleaning
- injection molding
- ion exchange
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- 238000000034 method Methods 0.000 title claims abstract description 87
- 239000004033 plastic Substances 0.000 title claims abstract description 75
- 229920003023 plastic Polymers 0.000 title claims abstract description 75
- 238000001465 metallisation Methods 0.000 title abstract description 9
- 238000004140 cleaning Methods 0.000 claims abstract description 111
- 238000005342 ion exchange Methods 0.000 claims abstract description 88
- 238000005406 washing Methods 0.000 claims abstract description 78
- 230000009467 reduction Effects 0.000 claims abstract description 63
- 239000002253 acid Substances 0.000 claims abstract description 43
- 230000000977 initiatory effect Effects 0.000 claims abstract description 43
- 239000007788 liquid Substances 0.000 claims abstract description 37
- 239000006227 byproduct Substances 0.000 claims abstract description 30
- 239000003513 alkali Substances 0.000 claims abstract description 14
- 239000000243 solution Substances 0.000 claims description 130
- 150000002500 ions Chemical class 0.000 claims description 92
- 239000000047 product Substances 0.000 claims description 89
- 238000001746 injection moulding Methods 0.000 claims description 76
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 58
- 229910001385 heavy metal Inorganic materials 0.000 claims description 48
- 239000012670 alkaline solution Substances 0.000 claims description 47
- 238000005238 degreasing Methods 0.000 claims description 41
- 238000005554 pickling Methods 0.000 claims description 40
- 229910052802 copper Inorganic materials 0.000 claims description 33
- 239000010949 copper Substances 0.000 claims description 33
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 32
- 239000003999 initiator Substances 0.000 claims description 29
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 28
- 238000001035 drying Methods 0.000 claims description 27
- 239000003960 organic solvent Substances 0.000 claims description 26
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000003929 acidic solution Substances 0.000 claims description 18
- 238000000151 deposition Methods 0.000 claims description 16
- 230000008021 deposition Effects 0.000 claims description 16
- 229910052786 argon Inorganic materials 0.000 claims description 12
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 12
- 238000011946 reduction process Methods 0.000 claims description 12
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 12
- 238000005507 spraying Methods 0.000 claims description 12
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 238000002347 injection Methods 0.000 claims description 8
- 239000007924 injection Substances 0.000 claims description 8
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 6
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 6
- 229940071870 hydroiodic acid Drugs 0.000 claims description 6
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 6
- 239000012279 sodium borohydride Substances 0.000 claims description 6
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 6
- ABKQFSYGIHQQLS-UHFFFAOYSA-J sodium tetrachloropalladate Chemical compound [Na+].[Na+].Cl[Pd+2](Cl)(Cl)Cl ABKQFSYGIHQQLS-UHFFFAOYSA-J 0.000 claims description 6
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 5
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 239000013067 intermediate product Substances 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 3
- 230000001678 irradiating effect Effects 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 46
- 239000000178 monomer Substances 0.000 abstract description 8
- 230000009471 action Effects 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 78
- 239000008367 deionised water Substances 0.000 description 46
- 229910021641 deionized water Inorganic materials 0.000 description 46
- 238000007747 plating Methods 0.000 description 26
- 230000000694 effects Effects 0.000 description 20
- 239000000843 powder Substances 0.000 description 20
- 239000000126 substance Substances 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 17
- 238000004381 surface treatment Methods 0.000 description 13
- 238000005516 engineering process Methods 0.000 description 12
- 229910021645 metal ion Inorganic materials 0.000 description 12
- 239000012778 molding material Substances 0.000 description 12
- 230000035939 shock Effects 0.000 description 12
- 239000000853 adhesive Substances 0.000 description 11
- 230000001070 adhesive effect Effects 0.000 description 11
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- 239000003344 environmental pollutant Substances 0.000 description 10
- 150000002894 organic compounds Chemical class 0.000 description 10
- 231100000719 pollutant Toxicity 0.000 description 10
- 238000002791 soaking Methods 0.000 description 10
- 229920001577 copolymer Polymers 0.000 description 9
- 229920001519 homopolymer Polymers 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- -1 t-butyl peroxy (2-ethyl) hexanoate Chemical compound 0.000 description 9
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 8
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 8
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000009832 plasma treatment Methods 0.000 description 6
- 150000003254 radicals Chemical class 0.000 description 6
- 239000012965 benzophenone Substances 0.000 description 5
- 230000004071 biological effect Effects 0.000 description 5
- 238000005336 cracking Methods 0.000 description 5
- 150000002170 ethers Chemical class 0.000 description 5
- 150000002484 inorganic compounds Chemical class 0.000 description 5
- 229910010272 inorganic material Inorganic materials 0.000 description 5
- 229920000620 organic polymer Polymers 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 229940051841 polyoxyethylene ether Drugs 0.000 description 5
- 229920000056 polyoxyethylene ether Polymers 0.000 description 5
- 229920006337 unsaturated polyester resin Polymers 0.000 description 5
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 4
- PCXCAXQEJCXNCY-UHFFFAOYSA-N CCc1cnc(CC)c(CC)c1CC Chemical compound CCc1cnc(CC)c(CC)c1CC PCXCAXQEJCXNCY-UHFFFAOYSA-N 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 3
- 239000006223 plastic coating Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 2
- 239000002894 chemical waste Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 125000000373 fatty alcohol group Chemical group 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- OVBJJZOQPCKUOR-UHFFFAOYSA-L EDTA disodium salt dihydrate Chemical compound O.O.[Na+].[Na+].[O-]C(=O)C[NH+](CC([O-])=O)CC[NH+](CC([O-])=O)CC([O-])=O OVBJJZOQPCKUOR-UHFFFAOYSA-L 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000008365 aromatic ketones Chemical class 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000000852 hydrogen donor Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 235000012249 potassium ferrocyanide Nutrition 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
- C23C18/2026—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by radiant energy
- C23C18/204—Radiation, e.g. UV, laser
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/06—Coating with compositions not containing macromolecular substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/123—Treatment by wave energy or particle radiation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/16—Chemical modification with polymerisable compounds
- C08J7/18—Chemical modification with polymerisable compounds using wave energy or particle radiation
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
- C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
- C23C18/2073—Multistep pretreatment
- C23C18/2086—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2300/00—Characterised by the use of unspecified polymers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention discloses a high-efficiency plastic photo-grafting treatment method, which comprises the following steps of: pretreatment, light grafting and post-treatment; the pretreatment step comprises plasma cleaning; the photo grafting comprises ultraviolet light initiation and ultraviolet light grafting; the post-treatment step comprises alkali washing, acid washing, ion exchange and ion reduction; the ion exchange and the ion reduction are both carried out in ultrasonic waves. According to the invention, the pretreatment and the post-treatment are respectively carried out before and after the plastic photo-grafting, so that the subsequent initiation and grafting efficiency is improved after the pretreatment; the post-treatment is carried out under the action of ultrasonic waves, so that byproducts and residual grafting liquid monomers generated in the grafting process can be eliminated, and the influence on the integrity of subsequent plastic surface metallization is avoided.
Description
Technical Field
The invention relates to the technical field of plastic surface treatment, in particular to a high-efficiency plastic photo-grafting treatment method and a plastic metallization method.
Background
Plastic metallization is a way to obtain a metal layer on the surface of plastic by adopting a specific treatment method, so that the surface of the plastic presents metal characteristics, thereby facilitating welding and electroplating; can replace metal products in some special fields, thereby reducing the cost and improving the product performance. The plastic metallization includes dry plating (physical vapor deposition, chemical vapor deposition), wet plating (chemical plating, electroplating, etc.) and photo-grafting; the photografting technology can avoid roughening a large amount of chromic acid and other high-pollution substances on the surface of the plastic, and has excellent environmental protection performance and low cost. The photografting is to use aromatic ketone and derivative to absorb ultraviolet light and then excite to a singlet state S, then quickly jump to a triplet state T, when the surface of the polymer is a hydrogen donor, carbonyl takes hydrogen to be reduced into hydroxyl, and a surface free radical is generated.
The plastic photografting is researched by students in China, related documents and patents also report that the influence of initiator concentration, initiation time, grafting liquid concentration and grafting time on the grafting rate is mainly researched, but the plastic photografting has a bottleneck on further improving the binding force of a metal plating layer, which is probably because byproducts generated in the grafting process are homopolymers, copolymers and grafting monomers, and the homopolymers and the copolymers are required to reduce the binding force of the plating layer, so that the binding force is not required by the metallization of the plastic surface, and the integrity of the subsequent copper plating effect is influenced by the post-grafting treatment. In addition, the existing plastic photo-grafting method only stays in a laboratory and cannot realize mass production; when the plastic photografting is carried out in a laboratory, the pretreatment of the plastic surface is carried out by simply removing oil by acid, and the plastic surface treatment mode is very simple. The research shows that the pretreatment and the post-treatment of the plastic surface play a very critical decisive role in metallizing the whole plastic surface, the initiation effect of the plastic surface is directly determined by the pre-treatment in the early stage, and the bonding strength of the metal coating is affected by the existence of grafting byproducts in the grafting post-treatment, so that the bonding force of the coating is improved by breaking through the two factors; in addition, the existing plastic photo-grafting method only stays in a laboratory stage, and for a production enterprise, cost problems are also required to be considered in the pretreatment and post-treatment processes of plastic photo-grafting in the process of putting into mass production.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a high-efficiency plastic photografting treatment method and a plastic metallization method.
The aim of the invention is achieved by the following technical scheme: the efficient plastic photo-grafting treatment method comprises the following steps of: pretreatment, light grafting and post-treatment;
the pretreatment step comprises plasma cleaning;
the photo grafting comprises ultraviolet light initiation and ultraviolet light grafting;
the post-treatment step comprises alkali washing, acid washing, ion exchange and ion reduction; the ion exchange and the ion reduction are both carried out in ultrasonic waves;
in the invention, the product after injection molding is subjected to pretreatment by adopting plasma cleaning, and during the plasma cleaning process, argon is utilized to bombard and clean the surface of the injection molding material, so that the polluted impurities on the surface of the injection molding material are sucked away by a vacuum pump along with air flow, and no chemical reaction exists in the plasma cleaning process, and the surface of the cleaned material is free of oxides, thus the purity after cleaning can be well maintained, the anisotropy of the material is ensured, the adhesive force of the surface of the material is increased, and the activity of the surface of the material is improved; the plasma treatment is adopted to ensure that the early initiator can be paved on the product, so that the initiation efficiency of the plastic surface can be greatly improved, and conditions are provided for subsequent uniform grafting; according to the invention, the surface treatment is carried out on the plastic material by utilizing a plasma technology, the structural surface of the plastic material is maximized under the bombardment of high-speed high-energy plasma, and meanwhile, an active layer is formed on the surface of the material, so that the adhesion force of the surface of the material is facilitated, no harmful substances are generated before and after the treatment, the treatment effect is good, the efficiency is high, and the operation cost is low; after post-treatment is carried out on the grafted product, the integrity of the subsequent electroless copper plating and higher binding force are ensured; wherein, in the alkaline washing step, an alkaline solution is utilized to react with acidic byproducts, and monomer acrylic acid can be polymerized to generate polyacrylic acid under the action of ultraviolet light, and an acid-base neutralization principle is utilized to effectively remove unavoidable homopolymers and copolymers in the grafting process, thereby improving the subsequent heavy metal ion exchange rate; in the alkaline washing and acid washing processes, the process can be carried out in ultrasonic waves, and the solution is more contacted with the surface under the vibration of the ultrasonic waves, so that the reaction is more complete, and byproducts and acid-base residues generated in the grafting process are eliminated; the ion exchange step is to place the product in heavy metal ion solution for ion exchange, the process is carried out in ultrasonic wave, the periodical instantaneous pressure in the liquid is reduced by utilizing the ultrasonic wave, a plurality of very small vacuum cavitation bubbles are generated, strong shock waves are generated when the vacuum cavitation bubbles are broken, and bubbles in the ion exchange process are eliminated; the heavy metal ion solution is fully contacted with the surface of the product, the metal ion exchange rate is improved, the metal ion exchange time is reduced, and the integrity of the subsequent electroless copper deposition is improved; the ionic reduction step is to put the product into a reducing solution, the process is carried out in ultrasonic waves, the ultrasonic waves are utilized to reduce the periodical instant pressure in the liquid, a plurality of very small vacuum cavitation bubbles are generated, strong shock waves are generated when the vacuum cavitation bubbles are broken, and bubbles in the ionic reduction process are eliminated; the reducing solution is fully contacted with the surface of the product, the reduction rate is improved, the reduction time is reduced, the integrity of the subsequent electroless copper plating is improved, and the production efficiency is improved.
The pretreatment step also comprises stress relief, oil removal, acid washing and drying; wherein,
the stress relief step is to soak the injection molding in an organic solvent; the volume fraction of the organic solvent is 20% -50%; the soaking time is 20 min-60 min; the organic solvent is preferably acetone; stress can be eliminated by soaking in an organic solvent, and the stress directly affects the surface cracking and buckling deformation of the material, so that the initiation and grafting of the surface of a product are not facilitated;
the step of degreasing is to put the injection molding into degreasing solution for cleaning; in the embodiment, the oil removing solution comprises oil removing powder, wherein the oil removing powder can be fatty alcohol polyoxyethylene ether series, alkylphenol polyoxyethylene ether series or a mixture of the two; the mass concentration of the oil removing solution is 20 g/L-60 g/L; the oil removal temperature is 50-70 ℃; the oil removal time is 30-90 min; the degreasing step can select proper solution, temperature and time to remove oily pollutants remained on the injection molding, wherein the oily pollutants are unfavorable for subsequent initiation and grafting;
the pickling step is to put the injection molding into pickling solution for cleaning; the method further comprises deionized cleaning, namely cleaning residual organic solvent and degreasing solution before the pickling step after the degreasing step; the temperature of deionized water cleaning is 50-90 ℃; the acid washing solution contains degreasing powder and dilute sulfuric acid; the volume fraction of the degreasing powder is 5-20%, the volume fraction of the dilute sulfuric acid is 5-15%, the pickling temperature is 20-50 ℃ and the pickling time is 5-20 min; after the pickling step, the method further comprises the step of washing with deionized water, wherein the temperature of washing with the deionized water is 50-90 ℃;
The drying step is that the injection molding product is put into an oven for drying; the drying temperature is 80-120 ℃ and the drying time is 10-30 min.
The plasma cleaning step is to place the injection molding product in a plasma cleaning machine, adopt argon gas for plasma cleaning, and cool with nitrogen gas; the cleaning time is 10 min-30 min; the vacuum degree of the plasma machine is controlled to be about 100Pa; the material is subjected to surface treatment by utilizing a plasma technology, the surface of the material structure is maximized under the bombardment of high-speed high-energy plasma, and meanwhile, an active layer is formed on the surface of the material, so that the adhesive force of the surface of the material is facilitated, the operation is simple, no harmful substances are generated before and after the treatment, the treatment effect is good, the efficiency is high, and the operation cost is low.
The ultraviolet light initiation step is as follows: spraying an initiator on the injection molding after the pretreatment, and then carrying out ultraviolet irradiation; the initiator concentration is controlled to be 0.5 g/L-5 g/L, the initiation time is 1 min-10 min, and the wavelength of the ultraviolet lamp is controlled to be 270 nm-380 nm; the initiator is a substance that activates a monomer molecule or a low molecule having a double bond in a linear molecular chain to form a radical and performs a chain reaction in the polymerization reaction. The initiator is usually an organic compound having an unsaturated polyester resin such as t-butyl peroxybenzoate (TBTB), t-butyl peroxy (2-ethyl) hexanoate (TBPO), benzophenone Peroxide (BPO), tetraethylpyridine, etc.
The ultraviolet grafting step comprises the following steps: spraying grafting liquid on the injection molding after ultraviolet initiation, and then carrying out ultraviolet irradiation; the concentration of the grafting liquid is controlled between 1g/L and 5g/L, the grafting time is controlled between 1min and 10min, the wavelength of an ultraviolet lamp is controlled between 270nm and 380nm, and the grafting liquid is a chemical reaction to convert organic compounds and inorganic compounds into organic molecules or organic polymers with similar biological activity. The grafting liquid mainly comprises acrylic acid, acrylonitrile, maleic anhydride, methacrylic acid or a mixture of the acrylic acid and the maleic anhydride, and the methacrylic acid.
In the post-treatment step, deionized cleaning is further included between alkali cleaning and acid cleaning; wherein, the alkaline washing step is to dissolve byproducts of the photografting process product by using alkaline solution; using alkaline solution with a certain concentration to dissolve byproducts in the ultraviolet grafting process on the product, wherein the byproducts directly affect the subsequent heavy metal ion exchange; the concentration of the alkaline solution is controlled to be 0.1 mol/L-1 mol/L, and the alkaline washing time is 1 min-10 min; the alkaline solution can be one or more of sodium hydroxide solution, potassium hydroxide solution, sodium carbonate and sodium bicarbonate solution; washing alkaline solution by deionized water; the alkaline solution acid washing step of washing residual alkaline solution by deionized water at normal temperature is to neutralize the alkaline solution in the alkaline washing step by an acid solution; the alkaline solution of the previous step can be neutralized with an acidic solution; the concentration of the acid solution is controlled to be 0.1 mol/L-1 mol/L, and the pickling time is 1 min-10 min; the acidic solution can be one or more of sulfuric acid, hydrochloric acid and phosphoric acid.
The ion exchange step is as follows: placing the injection molding product from which the photo-grafting byproducts are removed in a heavy metal ion solution for ion exchange; and after the ion exchange step and before the ion reduction step, deionized water is used for cleaning, and the residual heavy metal ion solution is washed by the deionized water at normal temperature.
The heavy metal ion solution comprises one or more of silver nitrate, palladium dichloride, sodium tetrachloropalladate and tetraammine palladium dichloride; the concentration of ions in the heavy metal ion solution is 0.1 mol/L-1 mol/L; in the ion exchange process, the ultrasonic frequency is 20 KHz-50 KHz, and the ultrasonic water temperature is 40 ℃ to 80 ℃; the ion exchange time is 4 min-10 min.
The ion reduction step is as follows: placing the ion-exchanged injection molding product into a reducing solution for ion reduction; after the ion reduction step, deionized water is used for cleaning, and the residual reducing solution is washed by the deionized water at normal temperature.
The reducing solution comprises one or more of hydrazine hydrate, sodium borohydride and hydroiodic acid; the concentration of the reducing solution is 0.1 mol/L-1 mol/L; in the ion reduction process, the ultrasonic frequency is controlled at 20 KHz-50 KHz, the ultrasonic water temperature is controlled at 40 ℃ to 80 ℃, and the ion reduction time is 4 min-10 min.
The invention has the following advantages:
1. the product after injection molding is subjected to pretreatment by adopting plasma cleaning, and during the plasma cleaning process, argon is utilized to bombard and clean the surface of the injection molding material, so that the polluted impurities on the surface of the injection molding material are sucked away by a vacuum pump along with air flow, no chemical reaction exists in the plasma cleaning process, and the surface of the cleaned material is free of oxides, so that the purity of the cleaned material can be well maintained, the anisotropism of the material is ensured, the adhesive force of the surface of the material is increased, and the activity of the surface of the material is improved; the plasma treatment is adopted to ensure that the early initiator can be paved on the product, so that the initiation efficiency of the plastic surface can be greatly improved, and conditions are provided for subsequent uniform grafting;
2. according to the invention, the surface treatment is carried out on the plastic material by utilizing a plasma technology, the structural surface of the plastic material is maximized under the bombardment of high-speed high-energy plasma, and meanwhile, an active layer is formed on the surface of the material, so that the adhesion force of the surface of the material is facilitated, no harmful substances are generated before and after the treatment, the treatment effect is good, the efficiency is high, and the operation cost is low;
3. after post-treatment is carried out on the grafted product, the integrity of the subsequent electroless copper plating and higher binding force are ensured; wherein, the steps of alkali washing and acid washing can effectively remove the unavoidable homopolymer and copolymer in the grafting process, thereby improving the subsequent heavy metal ion exchange rate; according to the invention, alkaline solution with proper concentration is selected for cleaning, homopolymer and copolymer can be removed, and then acid-washed acidic solution is utilized for neutralization, so that the subsequent ion exchange is not influenced by the existence of alkaline solution cations, meanwhile, the alkaline solution is selected, the pH value is not required to be regulated by a large amount of acidic solution after the pH value rises too fast, and a large amount of acid liquor is not wasted for neutralization to generate a large amount of chemical waste liquid;
4. The ion exchange step is to place the product in heavy metal ion solution for ion exchange, the process is carried out in ultrasonic wave, the periodical instantaneous pressure in the liquid is reduced by utilizing the ultrasonic wave, a plurality of very small vacuum cavitation bubbles are generated, strong shock waves are generated when the vacuum cavitation bubbles are broken, and bubbles in the ion exchange process are eliminated; the heavy metal ion solution is fully contacted with the surface of the product, the metal ion exchange rate is improved, the metal ion exchange time is reduced, the heavy metal ions are replaced to the grafted product through an ion exchange step, and then the heavy metal ions are reduced to metal simple substances through an ion reduction step, so that heavy metal-copper intermetallic compounds can be formed on the surface of the plastic during copper deposition, and the stability of the plating layer on the surface of the plastic is improved;
5. the ionic reduction step is to put the product into a reducing solution, the process is carried out in ultrasonic waves, the ultrasonic waves are utilized to reduce the periodical instant pressure in the liquid, a plurality of very small vacuum cavitation bubbles are generated, strong shock waves are generated when the vacuum cavitation bubbles are broken, and bubbles in the ionic reduction process are eliminated; the reducing solution is fully contacted with the surface of the product, the reduction rate is improved, the reduction time is reduced, the integrity of the subsequent electroless copper plating is improved, and the production efficiency is improved.
Drawings
Fig. 1 is a schematic diagram of the structure of an injection molded article.
FIG. 2 is a graph showing the effect of the surface of the injection molded article after copper plating.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. The components of the embodiments of the present invention generally described and illustrated in the figures herein may be arranged and designed in a wide variety of different configurations.
Thus, the following detailed description of the embodiments of the invention, as presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, based on the embodiments of the invention, which are apparent to those of ordinary skill in the art without inventive faculty, are intended to be within the scope of the invention.
In addition, the embodiments of the present invention and the features of the embodiments may be combined with each other without collision.
It should be noted that: like reference numerals and letters denote like items in the following figures, and thus once an item is defined in one figure, no further definition or explanation thereof is necessary in the following figures.
In the description of the present invention, it should be noted that, directions or positional relationships indicated by terms such as "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc., are directions or positional relationships based on those shown in the drawings, or are directions or positional relationships conventionally put in use of the inventive product, or are directions or positional relationships conventionally understood by those skilled in the art, are merely for convenience of describing the present invention and for simplifying the description, and are not to indicate or imply that the apparatus or element to be referred to must have a specific direction, be constructed and operated in a specific direction, and thus should not be construed as limiting the present invention. Furthermore, the terms "first," "second," and the like, are used merely to distinguish between descriptions and should not be construed as indicating or implying relative importance.
In the description of the present invention, it should also be noted that, unless explicitly specified and limited otherwise, the terms "disposed," "mounted," "connected," and "connected" are to be construed broadly, and may be, for example, fixedly connected, detachably connected, or integrally connected; can be mechanically or electrically connected; can be directly connected or indirectly connected through an intermediate medium, and can be communication between two elements. The specific meaning of the above terms in the present invention will be understood in specific cases by those of ordinary skill in the art.
Example 1: as shown in FIG. 1, the efficient plastic photo-grafting treatment method comprises the following steps of: pretreatment, light grafting and post-treatment;
the pretreatment step comprises plasma cleaning;
the photo grafting comprises ultraviolet light initiation and ultraviolet light grafting;
the post-treatment step comprises alkali washing, acid washing, ion exchange and ion reduction; the ion exchange and the ion reduction are both carried out in ultrasonic waves;
in the embodiment, the product after injection molding is subjected to pretreatment by adopting plasma cleaning, and during the plasma cleaning process, argon is utilized to bombard and clean the surface of the injection molding material, so that contaminated impurities on the surface of the injection molding material are sucked away by a vacuum pump along with air flow, no chemical reaction exists in the plasma cleaning process, and the surface of the cleaned material is free of oxides, so that the purity of the cleaned material can be well maintained, the anisotropy of the material is ensured, the adhesive force of the surface of the material is increased, and the activity of the surface of the material is improved; the plasma treatment is adopted to ensure that the early initiator can be paved on the product, so that the initiation efficiency of the plastic surface can be greatly improved, and conditions are provided for subsequent uniform grafting; according to the invention, the surface treatment is carried out on the plastic material by utilizing a plasma technology, the structural surface of the plastic material is maximized under the bombardment of high-speed high-energy plasma, and meanwhile, an active layer is formed on the surface of the material, so that the adhesion force of the surface of the material is facilitated, no harmful substances are generated before and after the treatment, the treatment effect is good, the efficiency is high, and the operation cost is low; after post-treatment is carried out on the grafted product, the integrity of the subsequent electroless copper plating and higher binding force are ensured; the step of removing the photo-grafting byproducts can effectively remove the unavoidable homopolymers and copolymers in the grafting process, so that the subsequent heavy metal ion exchange rate is improved; the ion exchange step is to place the product in heavy metal ion solution for ion exchange, the process is carried out in ultrasonic wave, the periodical instantaneous pressure in the liquid is reduced by utilizing the ultrasonic wave, a plurality of very small vacuum cavitation bubbles are generated, strong shock waves are generated when the vacuum cavitation bubbles are broken, and bubbles in the ion exchange process are eliminated; the heavy metal ion solution is fully contacted with the surface of the product, the metal ion exchange rate is improved, the metal ion exchange time is reduced, and the integrity of the subsequent electroless copper deposition is improved; the ionic reduction step is to put the product into a reducing solution, the process is carried out in ultrasonic waves, the ultrasonic waves are utilized to reduce the periodical instant pressure in the liquid, a plurality of very small vacuum cavitation bubbles are generated, strong shock waves are generated when the vacuum cavitation bubbles are broken, and bubbles in the ionic reduction process are eliminated; the reducing solution is fully contacted with the surface of the product, the reduction rate is improved, the reduction time is reduced, the integrity of the subsequent electroless copper plating is improved, and the production efficiency is improved.
The pretreatment step also comprises stress relief, oil removal, acid washing and drying; wherein,
the stress relief step is to soak the injection molding in an organic solvent; the volume fraction of the organic solvent is 20% -50%; the soaking time is 20 min-60 min; the organic solvent is preferably acetone; stress can be eliminated by soaking in an organic solvent, and the stress directly affects the surface cracking and buckling deformation of the material, so that the initiation and grafting of the surface of a product are not facilitated;
the step of degreasing is to put the injection molding into degreasing solution for cleaning; in the embodiment, the oil removing solution comprises oil removing powder, wherein the oil removing powder can be fatty alcohol polyoxyethylene ether series, alkylphenol polyoxyethylene ether series or a mixture of the two; the mass concentration of the oil removing solution is 20 g/L-60 g/L; the oil removal temperature is 50-70 ℃; the oil removal time is 30-90 min; the degreasing step can select proper solution, temperature and time to remove oily pollutants remained on the injection molding, wherein the oily pollutants are unfavorable for subsequent initiation and grafting;
the pickling step is to put the injection molding into pickling solution for cleaning; the method further comprises deionized cleaning, namely cleaning residual organic solvent and degreasing solution before the pickling step after the degreasing step; the temperature of deionized water cleaning is 50-90 ℃; the acid washing solution contains degreasing powder and dilute sulfuric acid; the volume fraction of the degreasing powder is 5-20%, the volume fraction of the dilute sulfuric acid is 5-15%, the pickling temperature is 20-50 ℃ and the pickling time is 5-20 min; after the pickling step, the method further comprises the step of washing with deionized water, wherein the temperature of washing with the deionized water is 50-90 ℃;
The drying step is that the injection molding product is put into an oven for drying; the drying temperature is 80-120 ℃ and the drying time is 10-30 min.
The plasma cleaning step is to place the injection molding product in a plasma cleaning machine, adopt argon gas for plasma cleaning, and cool with nitrogen gas; the cleaning time is 10 min-30 min; the vacuum degree of the plasma machine is controlled to be about 100Pa; the material is subjected to surface treatment by utilizing a plasma technology, the surface of the material structure is maximized under the bombardment of high-speed high-energy plasma, and meanwhile, an active layer is formed on the surface of the material, so that the adhesive force of the surface of the material is facilitated, the operation is simple, no harmful substances are generated before and after the treatment, the treatment effect is good, the efficiency is high, and the operation cost is low.
The ultraviolet light initiation step is as follows: spraying an initiator on the injection molding after the pretreatment, and then carrying out ultraviolet irradiation; the initiator concentration is controlled to be 0.5 g/L-5 g/L, the initiation time is 1 min-10 min, and the wavelength of the ultraviolet lamp is controlled to be 270 nm-380 nm; the initiator is a substance that activates a monomer molecule or a low molecule having a double bond in a linear molecular chain to form a radical and performs a chain reaction in the polymerization reaction. The initiator is usually an organic compound having an unsaturated polyester resin such as t-butyl peroxybenzoate (TBTB), t-butyl peroxy (2-ethyl) hexanoate (TBPO), benzophenone Peroxide (BPO), tetraethylpyridine, etc.;
The ultraviolet grafting step comprises the following steps: spraying grafting liquid on the injection molding after ultraviolet initiation, and then carrying out ultraviolet irradiation; the concentration of the grafting liquid is controlled between 1g/L and 5g/L, the grafting time is controlled between 1min and 10min, the wavelength of an ultraviolet lamp is controlled between 270nm and 380nm, and the grafting liquid is a chemical reaction to convert organic compounds and inorganic compounds into organic molecules or organic polymers with similar biological activity. The grafting liquid mainly comprises acrylic acid, acrylonitrile, maleic anhydride, methacrylic acid or a mixture of the acrylic acid and the maleic anhydride, and the methacrylic acid.
In the post-treatment step, deionized cleaning is further included between alkali cleaning and acid cleaning; wherein,
the alkaline washing step is to dissolve byproducts of the photografting process product by using an alkaline solution; dissolving byproducts in the ultraviolet grafting process on the product by using an alkaline solution, wherein the byproducts directly affect the subsequent heavy metal ion exchange; the concentration of the alkaline solution is controlled to be 0.1 mol/L-1 mol/L, and the alkaline washing time is 1 min-10 min; the alkaline solution can be one or more of sodium hydroxide solution, potassium hydroxide solution, sodium carbonate and sodium bicarbonate solution;
washing alkaline solution by deionized water; washing the residual alkaline solution by deionized water at normal temperature;
The acid washing step is to neutralize the alkaline solution in the alkaline washing step with an acidic solution; the alkaline solution of the previous step can be neutralized with an acidic solution; the concentration of the acid solution is controlled to be 0.1 mol/L-1 mol/L, and the pickling time is 1 min-10 min; the acidic solution can be one or more of sulfuric acid, hydrochloric acid and phosphoric acid.
The ion exchange step is as follows: placing the injection molding product from which the photo-grafting byproducts are removed in a heavy metal ion solution for ion exchange; and after the ion exchange step and before the ion reduction step, deionized water is used for cleaning, and the residual heavy metal ion solution is washed by the deionized water at normal temperature.
The heavy metal ion solution comprises one or more of silver nitrate, palladium dichloride, sodium tetrachloropalladate and tetraammine palladium dichloride; the concentration of ions in the heavy metal ion solution is 0.1 mol/L-1 mol/L; in the ion exchange process, the ultrasonic frequency is 20 KHz-50 KHz, and the ultrasonic water temperature is 40 ℃ to 80 ℃; the ion exchange time is 4 min-10 min.
The ion reduction step is as follows: placing the ion-exchanged injection molding product into a reducing solution for ion reduction; after the ion reduction step, deionized water is used for cleaning, and the residual reducing solution is washed by the deionized water at normal temperature.
The reducing solution comprises one or more of hydrazine hydrate, sodium borohydride and hydroiodic acid; the concentration of the reducing solution is 0.1 mol/L-1 mol/L; in the ion reduction process, the ultrasonic frequency is controlled to be 20 KHz-50 KHz, the ultrasonic water temperature is controlled to be 40 ℃ to 80 ℃, and the ion reduction time is 4 min-10 min;
example 2: as shown in FIG. 1, the efficient plastic photo-grafting treatment method comprises the following steps of: pretreatment, light grafting and post-treatment;
the pretreatment step comprises plasma cleaning;
the photo grafting comprises ultraviolet light initiation and ultraviolet light grafting;
the post-treatment step comprises alkali washing, acid washing, ion exchange and ion reduction; the ion exchange and the ion reduction are both carried out in ultrasonic waves;
in the embodiment, the product after injection molding is subjected to pretreatment by adopting plasma cleaning, and during the plasma cleaning process, argon is utilized to bombard and clean the surface of the injection molding material, so that contaminated impurities on the surface of the injection molding material are sucked away by a vacuum pump along with air flow, no chemical reaction exists in the plasma cleaning process, and the surface of the cleaned material is free of oxides, so that the purity of the cleaned material can be well maintained, the anisotropy of the material is ensured, the adhesive force of the surface of the material is increased, and the activity of the surface of the material is improved; the plasma treatment is adopted to ensure that the early initiator can be paved on the product, so that the initiation efficiency of the plastic surface can be greatly improved, and conditions are provided for subsequent uniform grafting; according to the invention, the surface treatment is carried out on the plastic material by utilizing a plasma technology, the structural surface of the plastic material is maximized under the bombardment of high-speed high-energy plasma, and meanwhile, an active layer is formed on the surface of the material, so that the adhesion force of the surface of the material is facilitated, no harmful substances are generated before and after the treatment, the treatment effect is good, the efficiency is high, and the operation cost is low; after post-treatment is carried out on the grafted product, the integrity of the subsequent electroless copper plating and higher binding force are ensured; the step of removing the photo-grafting byproducts can effectively remove the unavoidable homopolymers and copolymers in the grafting process, so that the subsequent heavy metal ion exchange rate is improved; the ion exchange step is to place the product in heavy metal ion solution for ion exchange, the process is carried out in ultrasonic wave, the periodical instantaneous pressure in the liquid is reduced by utilizing the ultrasonic wave, a plurality of very small vacuum cavitation bubbles are generated, strong shock waves are generated when the vacuum cavitation bubbles are broken, and bubbles in the ion exchange process are eliminated; the heavy metal ion solution is fully contacted with the surface of the product, the metal ion exchange rate is improved, the metal ion exchange time is reduced, and the integrity of the subsequent electroless copper deposition is improved; the ionic reduction step is to put the product into a reducing solution, the process is carried out in ultrasonic waves, the ultrasonic waves are utilized to reduce the periodical instant pressure in the liquid, a plurality of very small vacuum cavitation bubbles are generated, strong shock waves are generated when the vacuum cavitation bubbles are broken, and bubbles in the ionic reduction process are eliminated; the reducing solution is fully contacted with the surface of the product, the reduction rate is improved, the reduction time is reduced, the integrity of the subsequent electroless copper plating is improved, and the production efficiency is improved.
The pretreatment step also comprises stress relief, oil removal, acid washing and drying; wherein,
the stress relief step is to soak the injection molding in an organic solvent; the volume fraction of the organic solvent is 20%; the soaking time is 20min; the organic solvent is preferably acetone; stress can be eliminated by soaking in an organic solvent, and the stress directly affects the surface cracking and buckling deformation of the material, so that the initiation and grafting of the surface of a product are not facilitated;
the step of degreasing is to put the injection molding into degreasing solution for cleaning; in the embodiment, the oil removing solution comprises oil removing powder, wherein the oil removing powder is alkylphenol ethoxylates; the mass concentration of the oil removing solution is 20 g/L; the oil removal temperature is 50 ℃; the oil removal time is 30min; the degreasing step can select proper solution, temperature and time to remove oily pollutants remained on the injection molding, wherein the oily pollutants are unfavorable for subsequent initiation and grafting;
the pickling step is to put the injection molding into pickling solution for cleaning; the method further comprises deionized cleaning, namely cleaning residual organic solvent and degreasing solution before the pickling step after the degreasing step; the temperature of deionized water cleaning is 50 ℃; the acid washing solution contains degreasing powder and dilute sulfuric acid; the volume fraction of the degreasing powder is 5%, the volume fraction of the dilute sulfuric acid is 5%, the pickling temperature is 20 ℃, and the pickling time is 5min; after the pickling step, the method further comprises the step of washing with deionized water, wherein the temperature of washing with the deionized water is 50 ℃ for washing residual pickling solution;
The drying step is that the injection molding product is put into an oven for drying; the drying temperature was 80℃and the drying time was 10min.
The plasma cleaning step is to place the injection molding product in a plasma cleaning machine, adopt argon gas for plasma cleaning, and cool with nitrogen gas; the cleaning time is 10 min; the vacuum degree of the plasma machine is controlled to be about 100Pa; the material is subjected to surface treatment by utilizing a plasma technology, the surface of the material structure is maximized under the bombardment of high-speed high-energy plasma, and meanwhile, an active layer is formed on the surface of the material, so that the adhesive force of the surface of the material is facilitated, the operation is simple, no harmful substances are generated before and after the treatment, the treatment effect is good, the efficiency is high, and the operation cost is low.
The ultraviolet light initiation step is as follows: spraying an initiator on the injection molding after the pretreatment, and then carrying out ultraviolet irradiation; the initiator concentration is controlled at 0.5g/L, the initiation time is 1min, and the wavelength of the ultraviolet lamp is controlled at 270nm; the initiator is a substance that activates a monomer molecule or a low molecule having a double bond in a linear molecular chain to form a radical and performs a chain reaction in the polymerization reaction. The initiator is usually an organic compound having an unsaturated polyester resin such as t-butyl peroxybenzoate (TBTB), t-butyl peroxy (2-ethyl) hexanoate (TBPO), benzophenone Peroxide (BPO), tetraethylpyridine, etc.;
The ultraviolet grafting step comprises the following steps: spraying grafting liquid on the injection molding after ultraviolet initiation, and then carrying out ultraviolet irradiation; the concentration of the grafting liquid is controlled at 1g/L, the grafting time is controlled at 1min, the wavelength of the ultraviolet lamp is controlled at 270nm, and the grafting liquid is a chemical reaction to convert the organic compound and the inorganic compound into organic molecules or organic polymers with similar biological activity. The grafting liquid mainly comprises acrylic acid, acrylonitrile, maleic anhydride, methacrylic acid or a mixture of the acrylic acid and the maleic anhydride, and the methacrylic acid.
In the post-treatment step, deionized cleaning is further included between alkali cleaning and acid cleaning; wherein,
the alkaline washing step is to dissolve byproducts of the photografting process product by using an alkaline solution; in the embodiment, alkaline solution is used for dissolving byproducts in the ultraviolet irradiation process on the product, and the byproducts directly affect the subsequent heavy metal ion exchange; the concentration of the alkaline solution is controlled to be 0.1mol/L, and the alkaline washing time is 1min; the alkaline solution is sodium carbonate solution;
washing alkaline solution by deionized water; washing the residual alkaline solution by deionized water at normal temperature;
the acid washing step is to neutralize the alkaline solution in the alkaline washing step with an acidic solution; the alkaline solution of the previous step can be neutralized with an acidic solution; the concentration of the acid solution is controlled to be 0.1mol/L, and the pickling time is 1min; the acidic solution is hydrochloric acid.
The ion exchange step is as follows: placing the injection molding product from which the photo-grafting byproducts are removed in a heavy metal ion solution for ion exchange; and after the ion exchange step and before the ion reduction step, deionized water is used for cleaning, and the residual heavy metal ion solution is washed by the deionized water at normal temperature.
The heavy metal ion solution comprises one or more of silver nitrate, palladium dichloride, sodium tetrachloropalladate and tetraammine palladium dichloride; the concentration of ions in the heavy metal ion solution is 0.1 mol/L; in the ion exchange process, the ultrasonic frequency is 20 KHz, and the ultrasonic water temperature is 40 ℃; the ion exchange time was 4 min.
The ion reduction step is as follows: placing the ion-exchanged injection molding product into a reducing solution for ion reduction; after the ion reduction step, deionized water is used for cleaning, and the residual reducing solution is washed by the deionized water at normal temperature.
The reducing solution comprises one or more of hydrazine hydrate, sodium borohydride and hydroiodic acid; the concentration of the reducing solution is 0.1 mol/L; in the ion reduction process, the ultrasonic frequency is controlled at 20 KHz, the ultrasonic water temperature is controlled at 40 ℃, and the ion reduction time is 4 min.
Example 3: as shown in FIG. 1, the efficient plastic photo-grafting treatment method comprises the following steps of: pretreatment, light grafting and post-treatment;
the pretreatment step comprises plasma cleaning;
the photo grafting comprises ultraviolet light initiation and ultraviolet light grafting;
the post-treatment step comprises alkali washing, acid washing, ion exchange and ion reduction; the ion exchange and the ion reduction are both carried out in ultrasonic waves;
in the embodiment, the product after injection molding is subjected to pretreatment by adopting plasma cleaning, and during the plasma cleaning process, argon is utilized to bombard and clean the surface of the injection molding material, so that contaminated impurities on the surface of the injection molding material are sucked away by a vacuum pump along with air flow, no chemical reaction exists in the plasma cleaning process, and the surface of the cleaned material is free of oxides, so that the purity of the cleaned material can be well maintained, the anisotropy of the material is ensured, the adhesive force of the surface of the material is increased, and the activity of the surface of the material is improved; the plasma treatment is adopted to ensure that the early initiator can be paved on the product, so that the initiation efficiency of the plastic surface can be greatly improved, and conditions are provided for subsequent uniform grafting; according to the invention, the surface treatment is carried out on the plastic material by utilizing a plasma technology, the structural surface of the plastic material is maximized under the bombardment of high-speed high-energy plasma, and meanwhile, an active layer is formed on the surface of the material, so that the adhesion force of the surface of the material is facilitated, no harmful substances are generated before and after the treatment, the treatment effect is good, the efficiency is high, and the operation cost is low; after post-treatment is carried out on the grafted product, the integrity of the subsequent electroless copper plating and higher binding force are ensured; the step of removing the photo-grafting byproducts can effectively remove the unavoidable homopolymers and copolymers in the grafting process, so that the subsequent heavy metal ion exchange rate is improved; the ion exchange step is to place the product in heavy metal ion solution for ion exchange, the process is carried out in ultrasonic wave, the periodical instantaneous pressure in the liquid is reduced by utilizing the ultrasonic wave, a plurality of very small vacuum cavitation bubbles are generated, strong shock waves are generated when the vacuum cavitation bubbles are broken, and bubbles in the ion exchange process are eliminated; the heavy metal ion solution is fully contacted with the surface of the product, the metal ion exchange rate is improved, the metal ion exchange time is reduced, and the integrity of the subsequent electroless copper deposition is improved; the ionic reduction step is to put the product into a reducing solution, the process is carried out in ultrasonic waves, the ultrasonic waves are utilized to reduce the periodical instant pressure in the liquid, a plurality of very small vacuum cavitation bubbles are generated, strong shock waves are generated when the vacuum cavitation bubbles are broken, and bubbles in the ionic reduction process are eliminated; the reducing solution is fully contacted with the surface of the product, the reduction rate is improved, the reduction time is reduced, the integrity of the subsequent electroless copper plating is improved, and the production efficiency is improved.
The pretreatment step also comprises stress relief, oil removal, acid washing and drying; wherein,
the stress relief step is to soak the injection molding in an organic solvent; the volume fraction of the organic solvent is 50%; the soaking time is 60min; the organic solvent is preferably acetone; stress can be eliminated by soaking in an organic solvent, and the stress directly affects the surface cracking and buckling deformation of the material, so that the initiation and grafting of the surface of a product are not facilitated;
the step of degreasing is to put the injection molding into degreasing solution for cleaning; in this embodiment, the degreasing solution includes degreasing powder, and the degreasing powder may be fatty alcohol polyoxyethylene ether series; the mass concentration of the oil removing solution is 60 g/L; the oil removal temperature is 70 ℃; the oil removal time is 90min; the degreasing step can select proper solution, temperature and time to remove oily pollutants remained on the injection molding, wherein the oily pollutants are unfavorable for subsequent initiation and grafting;
the pickling step is to put the injection molding into pickling solution for cleaning; the method further comprises deionized cleaning, namely cleaning residual organic solvent and degreasing solution before the pickling step after the degreasing step; the temperature of deionized water cleaning is 90 ℃; the acid washing solution contains degreasing powder and dilute sulfuric acid; the volume fraction of the degreasing powder is 20%, the volume fraction of the dilute sulfuric acid is 15%, the pickling temperature is 50 ℃, and the pickling time is 20min; after the pickling step, the method further comprises the step of washing with deionized water, wherein the temperature of the washing with deionized water is 90 ℃ for washing residual pickling solution;
The drying step is that the injection molding product is put into an oven for drying; the drying temperature is 120 ℃ and the drying time is 30min.
The plasma cleaning step is to place the injection molding product in a plasma cleaning machine, adopt argon gas for plasma cleaning, and cool with nitrogen gas; the cleaning time is 30min; the vacuum degree of the plasma machine is controlled to be about 100Pa; the material is subjected to surface treatment by utilizing a plasma technology, the surface of the material structure is maximized under the bombardment of high-speed high-energy plasma, and meanwhile, an active layer is formed on the surface of the material, so that the adhesive force of the surface of the material is facilitated, the operation is simple, no harmful substances are generated before and after the treatment, the treatment effect is good, the efficiency is high, and the operation cost is low.
The ultraviolet light initiation step is as follows: spraying an initiator on the injection molding after the pretreatment, and then carrying out ultraviolet irradiation; the initiator concentration is controlled at 5g/L, the initiation time is 10min, and the wavelength of the ultraviolet lamp is controlled at 380nm; the initiator is a substance that activates a monomer molecule or a low molecule having a double bond in a linear molecular chain to form a radical and performs a chain reaction in the polymerization reaction. The initiator is usually an organic compound having an unsaturated polyester resin such as t-butyl peroxybenzoate (TBTB), t-butyl peroxy (2-ethyl) hexanoate (TBPO), benzophenone Peroxide (BPO), tetraethylpyridine, etc.;
The ultraviolet grafting step comprises the following steps: spraying grafting liquid on the injection molding after ultraviolet initiation, and then carrying out ultraviolet irradiation; the concentration of the grafting liquid is controlled at 5g/L, the grafting time is 10min, the wavelength of the ultraviolet lamp is controlled at 380nm, and the grafting liquid is a chemical reaction to convert the organic compound and the inorganic compound into organic molecules or organic polymers with similar biological activity. The grafting liquid mainly comprises acrylic acid, acrylonitrile, maleic anhydride, methacrylic acid or a mixture of the acrylic acid and the maleic anhydride, and the methacrylic acid.
In the post-treatment step, deionized cleaning is further included between alkali cleaning and acid cleaning; wherein,
the alkaline washing step is to dissolve byproducts of the photografting process product by using an alkaline solution; in the embodiment, alkaline solution is used for dissolving byproducts in the ultraviolet irradiation process on the product, and the byproducts directly affect the subsequent heavy metal ion exchange; the concentration of the alkaline solution is controlled at 1mol/L, and the alkaline washing time is 10min; the alkaline solution is a mixed solution of sodium hydroxide and sodium bicarbonate; the sodium bicarbonate and the sodium hydroxide are used together, so that the pH value is not required to be adjusted by a large amount of acid solution after the pH value rises too fast, and a large amount of acid solution is not wasted to neutralize and generate a large amount of chemical waste liquid;
Washing alkaline solution by deionized water; washing the residual alkaline solution by deionized water at normal temperature;
the acid washing step is to neutralize the alkaline solution in the alkaline washing step with an acidic solution; the alkaline solution of the previous step can be neutralized with an acidic solution; the concentration of the acid solution is controlled at 1mol/L, and the pickling time is 10min; the acidic solution is phosphoric acid.
The ion exchange step is as follows: placing the injection molding product from which the photo-grafting byproducts are removed in a heavy metal ion solution for ion exchange; and after the ion exchange step and before the ion reduction step, deionized water is used for cleaning, and the residual heavy metal ion solution is washed by the deionized water at normal temperature.
The heavy metal ion solution comprises one or more of silver nitrate, palladium dichloride, sodium tetrachloropalladate and tetraammine palladium dichloride; the concentration of ions in the heavy metal ion solution is 1mol/L; in the ion exchange process, the ultrasonic frequency is 50KHz, and the ultrasonic water temperature is 80 ℃; the ion exchange time was 10min.
The ion reduction step is as follows: placing the ion-exchanged injection molding product into a reducing solution for ion reduction; after the ion reduction step, deionized water is used for cleaning, and the residual reducing solution is washed by the deionized water at normal temperature.
The reducing solution comprises one or more of hydrazine hydrate, sodium borohydride and hydroiodic acid; the concentration of the reducing solution is 1mol/L; in the ion reduction process, the ultrasonic frequency is controlled at 50 KHz, the ultrasonic water temperature is controlled at 80 ℃, and the ion reduction time is 10min.
Example 4: as shown in FIG. 1, the efficient plastic photo-grafting treatment method comprises the following steps of: pretreatment, light grafting and post-treatment;
the pretreatment step comprises plasma cleaning;
the photo grafting comprises ultraviolet light initiation and ultraviolet light grafting;
the post-treatment step comprises alkali washing, acid washing, ion exchange and ion reduction; the ion exchange and the ion reduction are both carried out in ultrasonic waves;
in the embodiment, the product after injection molding is subjected to pretreatment by adopting plasma cleaning, and during the plasma cleaning process, argon is utilized to bombard and clean the surface of the injection molding material, so that contaminated impurities on the surface of the injection molding material are sucked away by a vacuum pump along with air flow, no chemical reaction exists in the plasma cleaning process, and the surface of the cleaned material is free of oxides, so that the purity of the cleaned material can be well maintained, the anisotropy of the material is ensured, the adhesive force of the surface of the material is increased, and the activity of the surface of the material is improved; the plasma treatment is adopted to ensure that the early initiator can be paved on the product, so that the initiation efficiency of the plastic surface can be greatly improved, and conditions are provided for subsequent uniform grafting; according to the invention, the surface treatment is carried out on the plastic material by utilizing a plasma technology, the structural surface of the plastic material is maximized under the bombardment of high-speed high-energy plasma, and meanwhile, an active layer is formed on the surface of the material, so that the adhesion force of the surface of the material is facilitated, no harmful substances are generated before and after the treatment, the treatment effect is good, the efficiency is high, and the operation cost is low; after post-treatment is carried out on the grafted product, the integrity of the subsequent electroless copper plating and higher binding force are ensured; the step of removing the photo-grafting byproducts can effectively remove the unavoidable homopolymers and copolymers in the grafting process, so that the subsequent heavy metal ion exchange rate is improved; the ion exchange step is to place the product in heavy metal ion solution for ion exchange, the process is carried out in ultrasonic wave, the periodical instantaneous pressure in the liquid is reduced by utilizing the ultrasonic wave, a plurality of very small vacuum cavitation bubbles are generated, strong shock waves are generated when the vacuum cavitation bubbles are broken, and bubbles in the ion exchange process are eliminated; the heavy metal ion solution is fully contacted with the surface of the product, the metal ion exchange rate is improved, the metal ion exchange time is reduced, and the integrity of the subsequent electroless copper deposition is improved; the ionic reduction step is to put the product into a reducing solution, the process is carried out in ultrasonic waves, the ultrasonic waves are utilized to reduce the periodical instant pressure in the liquid, a plurality of very small vacuum cavitation bubbles are generated, strong shock waves are generated when the vacuum cavitation bubbles are broken, and bubbles in the ionic reduction process are eliminated; the reducing solution is fully contacted with the surface of the product, the reduction rate is improved, the reduction time is reduced, the integrity of the subsequent electroless copper plating is improved, and the production efficiency is improved.
The pretreatment step also comprises stress relief, oil removal, acid washing and drying; wherein,
the stress relief step is to soak the injection molding in an organic solvent; the volume fraction of the organic solvent is 30%; the soaking time is 30min; the organic solvent is preferably acetone; stress can be eliminated by soaking in an organic solvent, and the stress directly affects the surface cracking and buckling deformation of the material, so that the initiation and grafting of the surface of a product are not facilitated;
the step of degreasing is to put the injection molding into degreasing solution for cleaning; in the embodiment, the oil removing solution comprises oil removing powder, wherein the oil removing powder is alkylphenol ethoxylates; the mass concentration of the oil removing solution is 40 g/L; the oil removal temperature is 55 ℃; the oil removal time is 60min; the degreasing step can select proper solution, temperature and time to remove oily pollutants remained on the injection molding, wherein the oily pollutants are unfavorable for subsequent initiation and grafting;
the pickling step is to put the injection molding into pickling solution for cleaning; the method further comprises deionized cleaning, namely cleaning residual organic solvent and degreasing solution before the pickling step after the degreasing step; the temperature of deionized water cleaning is 60 ℃; the acid washing solution contains degreasing powder and dilute sulfuric acid; the volume fraction of the degreasing powder is 15%, the volume fraction of the dilute sulfuric acid is 10%, the pickling temperature is 45 ℃, and the pickling time is 20min; after the pickling step, the method further comprises the step of washing with deionized water, wherein the temperature of washing with the deionized water is 60 ℃ for washing residual pickling solution;
The drying step is that the injection molding product is put into an oven for drying; the drying temperature is 100 ℃ and the drying time is 15min.
The plasma cleaning step is to place the injection molding product in a plasma cleaning machine, adopt argon gas for plasma cleaning, and cool with nitrogen gas; the cleaning time is 20min; the vacuum degree of the plasma machine is controlled to be about 100Pa; the material is subjected to surface treatment by utilizing a plasma technology, the surface of the material structure is maximized under the bombardment of high-speed high-energy plasma, and meanwhile, an active layer is formed on the surface of the material, so that the adhesive force of the surface of the material is facilitated, the operation is simple, no harmful substances are generated before and after the treatment, the treatment effect is good, the efficiency is high, and the operation cost is low.
The ultraviolet light initiation step is as follows: spraying an initiator on the injection molding after the pretreatment, and then carrying out ultraviolet irradiation; the initiator concentration is controlled at 1.0g/L, the initiation time is 5min, and the wavelength of the ultraviolet lamp is controlled at 355nm; the initiator is a substance that activates a monomer molecule or a low molecule having a double bond in a linear molecular chain to form a radical and performs a chain reaction in the polymerization reaction. The initiator is typically an organic compound having an unsaturated polyester resin, a preferred initiator being Benzophenone Peroxide (BPO);
The ultraviolet grafting step comprises the following steps: spraying grafting liquid on the injection molding after ultraviolet initiation, and then carrying out ultraviolet irradiation; the concentration of the grafting liquid is controlled at 3g/L, the grafting time is 6min, the wavelength of the ultraviolet lamp is controlled at 325nm, and the grafting liquid is a chemical reaction to convert the organic compound and the inorganic compound into organic molecules or organic polymers with similar biological activity. The grafting liquid is preferably acrylic acid.
In the post-treatment step, deionized cleaning is further included between alkali cleaning and acid cleaning; wherein,
the alkaline washing step is to dissolve byproducts of the photografting process product by using an alkaline solution; in the embodiment, alkaline solution is used for dissolving byproducts in the ultraviolet irradiation process on the product, and the byproducts directly affect the subsequent heavy metal ion exchange; the concentration of the alkaline solution is controlled to be 0.2 mol/L, and the alkaline washing time is 2min; the alkaline solution is sodium hydroxide;
washing alkaline solution by deionized water; washing the residual alkaline solution by deionized water at normal temperature;
the acid washing step is to neutralize the alkaline solution in the alkaline washing step with an acidic solution; the alkaline solution of the previous step can be neutralized with an acidic solution; the concentration of the acid solution is controlled to be 0.2 mol/L, and the pickling time is 2min; the acidic solution is sulfuric acid.
The ion exchange step is as follows: placing the injection molding product from which the photo-grafting byproducts are removed in a heavy metal ion solution for ion exchange; and after the ion exchange step and before the ion reduction step, deionized water is used for cleaning, and the residual heavy metal ion solution is washed by the deionized water at normal temperature.
The heavy metal ion solution comprises one or more of silver nitrate, palladium dichloride, sodium tetrachloropalladate and tetraammine palladium dichloride; the concentration of ions in the heavy metal ion solution is 0.5mol/L; in the ion exchange process, the ultrasonic frequency is 39KHz, and the ultrasonic water temperature is 60 ℃; the ion exchange time was 8min.
The ion reduction step is as follows: placing the ion-exchanged injection molding product into a reducing solution for ion reduction; after the ion reduction step, deionized water is used for cleaning, and the residual reducing solution is washed by the deionized water at normal temperature.
The reducing solution comprises one or more of hydrazine hydrate, sodium borohydride and hydroiodic acid; the concentration of the reducing solution is 0.5mol/L; in the ion reduction process, the ultrasonic frequency is controlled at 39KHz, the ultrasonic water temperature is controlled at 40-80 ℃, and the ion reduction time is 8min.
Example 5: a plastic metallization method comprises the steps of treating a plastic product by the efficient plastic photografting treatment method in the embodiment 4 to obtain an intermediate product; then carrying out electroless copper deposition on the intermediate product;
the electroless copper plating solution comprises CuSO4.5H2O with the mass concentration of 12 g/L; disodium ethylenediamine tetraacetate dihydrate with a mass concentration of 40 g/L; formaldehyde with volume concentration of 10 mL/L; sodium hydroxide with mass concentration of 12 g/L; bipyridine with the mass concentration of 12 mg/L; potassium hexacyanoferrate (II) trihydrate at a mass concentration of 90 mg/L; the pH is controlled at 12; the solution temperature was 55 ℃; the deposition speed is 5 mu m/h; wherein the mass percentage of formaldehyde is 40%.
Copper plating integrity: and the product after copper deposition is placed under a 200-time magnifying glass, no bubbles are observed on the surface of the product, and the copper plating integrity is good.
And (3) binding force characterization: the product is arranged on a tensile machine, a pull-off experiment is carried out by using a force vertical to the surface of a plating piece until the metal plating layer is separated from the plastic matrix, a tensile value (N) is recorded, and the peeling strength Fr can be obtained through calculation according to the following formula:
FH=N/S；
Fr=FH·σ3/4/5.5；
wherein FH is the pull-out strength (N/cm) 2 ) Fr is the peel strength (N/cm) of the plastic coating, and sigma is the thickness (cm) of the metal layer to be peeled; the strength of the plastic coating glass is the binding force.
Example 6: and testing the binding force of the plastic coating obtained by different treatment methods.
Experiment group 1: electroless copper deposition was performed in the manner of example 5.
Experiment group 2: electroless copper deposition was performed in the manner of example 5, except that the cleaning time of the plasma cleaning step was 10 minutes when the injection molded article was subjected to the efficient plastic photografting treatment.
Experiment group 3: electroless copper deposition was performed in the manner of example 5, except that the cleaning time of the plasma cleaning step was 30 minutes when the injection molded article was subjected to the efficient plastic photo-grafting treatment.
Experiment group 4: electroless copper deposition was performed in the manner of example 5, except that plasma cleaning was not included in the pretreatment step when the injection molded article was subjected to efficient plastic photografting.
Experimental group 5: electroless copper deposition was performed in the manner of example 5, except that after the high-efficiency plastic photografting treatment of the injection molded article, the post-treatment step was not performed with alkaline washing and acid washing steps, and the ion exchange and ion reduction were directly performed after washing with deionized water only.
Experiment group 6: electroless copper deposition was performed in the manner of example 5, except that in the post-treatment step, the ion exchange and ion reduction steps were not performed in ultrasonic waves at the time of performing efficient plastic photografting treatment on the injection molded article.
The pull-off force results of the obtained plastic metal plating of experimental groups 1 to 6 are shown in table 1 below.
Although the present invention has been described with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications may be made to the embodiments described, or equivalents may be substituted for elements thereof, and any modifications, equivalents, improvements and changes may be made without departing from the spirit and principles of the present invention.
Claims (10)
1. The efficient plastic photo-grafting treatment method is characterized by comprising the following steps of: pretreatment, light grafting and post-treatment;
the pretreatment step comprises plasma cleaning;
the photo grafting comprises ultraviolet light initiation and ultraviolet light grafting;
the post-treatment step comprises alkali washing, acid washing, ion exchange and ion reduction; the ion exchange and the ion reduction are both carried out in ultrasonic waves.
2. The method of claim 1, wherein the pretreatment step further comprises destressing, degreasing, acid washing and drying; wherein,
the stress relief step is to soak the injection molding in an organic solvent;
The step of degreasing is to put the injection molding into degreasing solution for cleaning;
the pickling step is to put the injection molding into pickling solution for cleaning;
the drying step is to dry the injection molding in an oven.
3. The efficient plastic photo-grafting treatment method according to claim 1, wherein: the plasma cleaning step is to place the injection molding product in a plasma cleaning machine, adopt argon gas for plasma cleaning, and cool with nitrogen gas; the cleaning time is 10 min-30 min.
4. The efficient plastic photo-grafting treatment method according to claim 1, wherein:
the ultraviolet light initiation step is as follows: spraying an initiator on the injection molding after the pretreatment, and then carrying out ultraviolet irradiation;
the ultraviolet grafting step comprises the following steps: spraying grafting liquid on the injection after ultraviolet initiation, and then irradiating with ultraviolet light.
5. The efficient plastic photo-grafting treatment method according to claim 1, wherein: in the post-treatment step, deionized cleaning is further included between alkali cleaning and acid cleaning; the alkaline washing adopts alkaline solution with the concentration of 0.1 mol/L-1 mol/L; the alkaline solution comprises one or more of sodium hydroxide solution, potassium hydroxide solution, sodium carbonate and sodium bicarbonate solution; the acid washing adopts an acidic solution with the concentration of 0.1mol/L to 1 mol/L; the acidic solution comprises one or more of sulfuric acid, hydrochloric acid and phosphoric acid.
6. The efficient plastic photo-grafting treatment method according to claim 1, wherein: the ion exchange step is as follows: and placing the injection molding product from which the photo-grafting byproducts are removed in a heavy metal ion solution for ion exchange.
7. The efficient plastic photo-grafting treatment method according to claim 6, wherein: the heavy metal ion solution comprises one or more of silver nitrate, palladium dichloride, sodium tetrachloropalladate and tetraammine palladium dichloride; the concentration of ions in the heavy metal ion solution is 0.1 mol/L-1 mol/L; in the ion exchange process, the ultrasonic frequency is 20 KHz-50 KHz, and the ultrasonic water temperature is 40 ℃ to 80 ℃; the ion exchange time is 4 min-10 min.
8. The efficient plastic photo-grafting treatment method according to claim 1, wherein: the ion reduction step is as follows: and placing the ion-exchanged injection molding product into a reducing solution for ion reduction.
9. The efficient plastic photo-grafting treatment method according to claim 8, wherein: the reducing solution comprises one or more of hydrazine hydrate, sodium borohydride and hydroiodic acid; the concentration of the reducing solution is 0.1 mol/L-1 mol/L; in the ion reduction process, the ultrasonic frequency is controlled at 20 KHz-50 KHz, the ultrasonic water temperature is controlled at 40 ℃ to 80 ℃, and the ion reduction time is 4 min-10 min.
10. A method for metallizing plastic, characterized by: treating a plastic product by the efficient plastic photografting treatment method according to any one of claims 1-9 to obtain an intermediate product; and then carrying out electroless copper deposition on the intermediate product.
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